Aminotriazine-aldehyde resins and process for preparation

ABSTRACT

A polyamino triazine, such as melamine or benzoguanamine, etc., is reacted with an aldehyde such as formaldehyde, and a vinyl compound containing two active hydrogens capable of reaction with an aldehyde or alkylol group in such a manner as not to react with or destroy the vinyl group. Typical vinyl-containing compounds are acrylamide, diacetone acrylamide, allylamine, etc. Mixtures of the resulting resins with polyester resins derived from a glycol and an unsaturated dibasic carboxylic acid are particularly useful. These resin mixtures are capable of being cured by free radical catalysts through the vinyl group to give improved properties. The resulting crosslinked products have excellent electrical properties and are particularly useful as molding compositions for encapsulating electrical parts, and also as binders in fiberreinforced plastics.

PROCESS FOR PREPARATION Phillip A. Waitkus, Sheboygan, Wis.

Plastics Engineering Company, Sheboygan, Wis.

Filed: Apr. 8, 1974 Appl. No.: 458,835

Related US. Application Data Continuation-in-part of Ser. No. 232,964, March 18, 1972, Pat. No. 3,839,289.

lnventor:

Assignee:

References Cited UNITED STATES PATENTS 10/1970 Ravve ll7/93.3l

United States Patent 1191 1111 3,887,637 Waitkus 1451 June 3, 1975 ,[54] AMINOTRIAZINE-ALDEHYDE RESINS AND 3,839,289 10/1974 Waitkus 260/64 Primary Examiner-Lester L. Lee Attorney, Agent, or Firm-Walter J. Monacelli [5 7] ABSTRACT A polyamino triazine, such as melamine or benzoguanamine, etc., is reacted with an aldehyde such as formaldehyde, and a vinyl compound containing two active hydrogens capable of reaction with an aldehyde or alkylol group in such a manner as not to react with or destroy the vinyl group. Typical vinyl-containing compounds are acrylamide, diacetone acrylamide, a1- lylamine, etc. Mixtures of the resulting resins with polyester resins derived from a glycol and an unsaturated dibasic carboxylic acid are particularly useful. These resin mixtures are capable of being cured by free radical catalysts through the vinyl group to give improved properties. The resulting crosslinked products have excellent electrical properties and are particularly useful as molding compositions for encapsulating electrical parts, and also as binders in fiberreinforced plastics.

21 Claims, N0 Drawings AMINOTRIAZINE-ALDEHYDE RESINS AND PROCESS FOR PREPARATION This application is a continuation-in-part of copending application Ser. No. 232,964, filed Mar. 18, 1972 now U.S. Pat. No. 3,839,289.

BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to an improved resin composition and the process for preparation thereof. More specifically, it relates to a resin prepared by the reaction of a triazine compound containing two or more NH groups by reaction with an aldehyde and an aldehyde reactible compound which also contains a vinyl group. Still more specifically, it relates to the production of resin compositions having vinyl groups therein capable of being crosslinked or cured by free radical-generating catalysts to produce products having excellent electrical properties.

2. State of the Prior Art Aldehyde condensation reactions used in producing melamine-formaldehyde and benzoguanamineformaldehyde resins proceed by the elimination of a condensation product, mainly water. In the latter stages of resinification or curing, the elimination of the condensation product. i.e. water, becomes more difficult and the curing is retarded by the difficulty in the elimination of water. Incomplete curing and susceptibility to hydrolysis results in gradual degradation of electrical properties.

STATEMENT OF THE INVENTION The resin of this invention comprises the reaction product of an amino-1,3.5-triazine compound containing two or more NH groups, particularly melamine and benzoguanamine, with an aldehyde, preferably formaldehyde, and a compound having a vinyl group and at least two active hydrogens capable of reacting with an aldehyde or an alkylol group. This vinyl-containing compound can be represented by the formula wherein:

R is preferably hydrogen but can also be a group which does not affect the ability of the double bond to enter into free radical addition reactions, such as an alkyl group of l-4 carbon atoms, an aryl radical of 6-8 carbon atoms such as phenyl, tolyl, xylyl or an aryl radical having one or two chloro or bromo atoms attached to the aromatic nucleus. and X represents a group having two or more active hydrogens therein capable of reacting with the aldehyde or an alkylol radical such as O O O etc., and also contains a vinyl group of the formula wherein R is hydrogen or an alkyl group of 1-4 carbon atoms, such as methyl, ethyl, propyl and butyl.

Diacetone acrylamide and acrylamide are preferred compounds, but also suitable for this purpose are vinyl amine, allyl amine, vinyl aniline, 2-amino propene, methyl vinyl ketone, ethyl vinyl ketone, methyl allyl ketone, etc. With such compounds the aldehyde is first reached with the amino or keto-activated methyl group leaving the vinyl group free and available for subsequent free radical-generated crosslinking.

The proportion of the vinyl-containing compound can vary depending on the amount of cross-linking through free radical generation desired in the ultimate composition. For most purposes, 0.05- moles, preferably 0.1 to 10 moles of the vinyl-containing compound may be used per mole of melamine or benzoquanamine. The amount of formaldehyde or other aldehyde is in the range of 0.5-6 moles of formaldehyde or other aldehyde per mole of melamine, etc., preferably 1.5-2.5, and also an additional amount of 0.5-5, preferably 1.5-3 moles of formaldehyde or other aldehyde, or aldehyde producing material, per mole of vinyl compound.

The condensation of the aldehyde with the amino groups is favored by basic conditions, preferably a pH of 7-8 initially, and toward the latter stages a pH in the range of 10-12.

The condensation is also favored by a reaction temperature of 60-100C., preferably about 85-95C. When the reaction has advanced to a stage where a drop of the reaction mass placed in cold water 15C.) will produce a slightly opaque cloud, the pH is adjusted to 10-1 1.5 and water removed from the reaction mass by reducing the pressure, gradually if necessary, to remove water by distillation at a controllable rate. This is continued until the resultant resin reaches a stage where it it hard and brittle enough to be ground to powder when cooled. This stage can be judged either by re moving and cooling a sample or by determining when the gradient bar melting point has reached about -200C.

The resins produced by the aldehyde condensation within the ratios specified may be either solid or liquid and are miscible in various solvents, depending upon the specific composition Solvents which are preferred, depending on the particular resin composition, include water, diallyl phthalate, styrene, divinyl benzene. triallyl cyanurate, diallyl itaconate, chlorostyrene, methyl methacrylate, butyleneglycoldimethacrylate, and various alcohols and ketones such as methanol, ethanol, isopropanol. acetone, methyl vinyl ketone, etc.

Solutions of the resins may be used to impregnate paper, cloth, asbestos or other reinforcing fibers, woven, or non-woven, by various methods known in the art. In the impregnation step free radical initiating catalysts such as benzoyl peroxide, dicumyl peroxide, etc., may be included in the solution to effect ultimate optimum cure in the molding or laminating cycle. The resulting treated web or fabric may then be dried to a tack-free but uncured state and stacked with other such sheets for ultimate molding or laminating for forming articles of various shapes such as sheet stock and dishware Various pressures may be used in the molding cycle although 50 to 1,000 psi are generally favored.

Because of the high speed of free radical reactions. the molded articles may be manufactured at much faster production rates than for aldehyde condensation moldings. These products can be made without special provision for elimination of water or other volatile materials as is generally required in condensation reactions to assure sound, voidfree parts. Moreover, the resins of this invention offer distinct advantages over the processing of conventional unsaturated polyester resins. These new resins require only steam heated reactors in contrast to the more complicated special boiler equipment required to produce high temperature conditions necessary for polyester processing. Moreover, the resin processing is more economical for these new resins since the cycle time generally does not exceed 6 hours, whereas standard polyester reactions required 14-20 hours for completion.

The condensation reaction by which the resins of this invention are produced may be illustrated as follows:

ii z wherein Z represents the triazine nucleus C N NH or C N ---C,;l-l as in melamine or benzoguanamine respectively;

R and X are as defined above; and

m and n are each integers having a value of at least 2 and their values are governed by the relative proportions of diamino and vinyl compounds used as well as the molecular weight to which the condensation reactions are conducted. The vinylcontaining repeating units may be interspersed at random between the amino-containing repeating units.

Depending on the proportions of various reagents used, the number of the respective repeating units in the resulting polymer will vary accordingly. If a high proportion of melamine to diacetone acrylaminde is used, then there will be in the polymer molecule a number of melamine groups bridged together by methylene radicals thereby forming a linear chain of melamine groups connected by methylene groups and periodically, in accordance with the proportion of diacetone acrylamide used, there will appear the corresponding diacetone acrylaminde repeating unit. If the proportion of formaldehyde to other components is high enough, crosslinkages between polymer chains may be effected between melamine radicals in two or more linear chains. As noted above, the vinyl groups in the repeating units shown above are available for free radical crosslinking.

The polymerization reaction may be illustrated more specifically by the reaction of melamine and diacetone acrylamide with formaldehyde in the ratio of one mole of melamine and two moles of formaldehyde per mole of diacetone acrylamide. The resulting polymer chain can be represented as follows:

The values of n and m should be approximately equal and the actual values depend on the extent to which the condensation reaction is continued.

While the repeating unit derived from the diacetone acrylamide is shown in the formula as having both valence bonds for attachment to methylene groups attached to the terminal carbon of the diacetone acrylamide, it is also possible that these bonds may be formed by replacement of hydrogen from the amino nitrogen and the methylene group next to the keto group. However, since these groups are both adjacent to the C(CH group and exposed to steric hindrance therefrom it is believed that the attachments are more likely to the terminal carbon as indicated. In any case it is intended that the above formula embraces possible attachments to these other sites. It is also intended that the respective repeating units may appear in various arrangements including regular alternation, random arrangement and with blocks of either appearing periodically.

It is possible also that a terminal repeating unit may have a hydrogen atom retained in place of the CH OH group shown above.

Since the diacetone acrylamide is relatively more expensive than the other components, it is generally preferable to use only as much as is capable of producing the desired crosslinking results. Generally 0.1-0.5 moles per mole of melamine is sufficient. Likewise the other vinyl-containing components may alsobe used in minor proportion particularly where they are relatively expensive.

The resins of this invention are particularly useful in improving the properties of other resins such as alkyd or unsaturated polyester resins. The polyester resins are susceptible to hydrolysis when exposed to high humidity for prolonged periods. Consequently the electrical properties deteriorate. By the addition of 1-9570, preferably 5-5070 by weight of the resins of this invention it is found that electrical properties are improved and that these properties are retained indefinitely even when exposed to high humidity.

In such mixtures, the are tracking resistance. are re-' sistance, and dielectric properties are of high quality. Moreover, in comparison with typical alkyds. the surface has a significantly harder finish when the amine copolymer of this invention is incorporated. This providcs improved wear and abrasion resistance which properties are particularly important where the molded product is to be used or as a moving part exposed to abrasive wear.

The inclusion of the amine resin also enhances the flame resistance and avoids the use or inclusion of halogenated compounds and antimony trioxide and thereby avoids the corrosive effect the halogenated materials have on electrical contacts and the high price of antimony compounds which are often used with the halogenated compounds.

The alkyd or polyester resins with which the resins of this invention are particularly useful are the condensation polymers of polyhydric alcohols, preferably aliphatic glycols having 2-10 carbon atoms, such as ethylene, propylene, hexamethylene, neopentyl glycols, diethylene and triethylene gylcols, dipropylene and tripropylene glycols, etc., with polybasic, preferably dibasic acids having 4-12 carbon atoms such as isophthalic, terephthalic, orthophthalic, naphthalene dicarboxyllic, diphenyl dicarboxyllic, maleic, fumaric. itaconic, methylmaleic, citraconic, succinic. adipic, etc. For the purpose of this invention the dibasic acid component comprises at least 5% preferably at least 25% of an unsaturated acid such as maleic or itaconic, and the other dibasic acids used in completing esterification may be free of ethylenic unsaturation.

For the purpose of this invention it is desirable that the acid and hydroxyl numbers of the polyester are as low as possible. However where adhesive properties are desired it is advantagous that the acid number is between 5 and 35.

general the acid number is -60, preferably -35, and the hydroxyl number is 0-180, preferably 30-80.

Fillers and modifiers can be used in such compositions including inorganic and organic fillers such as silica, wood flour, clays, diatomaceous earths, or fibrous fillers such as fibers of glass, asbestos, sisal, carbon, metals, etc., plasticizers or lubricants, such as zinc or calcium stearate, polyamide waxes, graphite, molybdenum disulfide, montan wax, carnuba wax, etc., pigment and coloring agents, such as carbon black and numerous hydrocarbon soluble organic dyes, as well as inorganic pigments such as titanium dioxide, cadmium yellow, etc. Curing agents including the various free radical generating catalysts such as the peroxy and am compounds well known in the art for this purpose. Particularly suitable for this purpose are benzoyl, t-butyl, dicumyl, lauroyl peroxides, etc., t-butyl hydroperoxide, t-butyl perbenzoate, azobisisobutyronitrile, etc. Generally 0.05l0 percent, preferably 0.1-5 percent catalyst is sufficient for the purpose.

It is also particularly advantageous to use 1-50%, preferably 5-30% of a polymerizable monomer as a solvent and to copolymerize the monomer and resin of this invention. Unsaturated polyesters, as indicated above, may also be present in the solution in the proportions indicated. Polymerizable monomer solvents suitable for this purpose are styrene, diallyl phthalate, divinyl benzene, triallyl cyanurate, diallyl itaconate, chlorostyrene, methyl vinyl ketone, acrylates such as methyl methacrylate, ethyleneglycol dimethacrylate, trimethylolpropane trimethacrylate, 1 ,3-butyleneglycol dimethacrylate, allyl methacrylate, etc.

Various methods of practicing the invention are illustrated by the following examples. These examples are intended merely to illustrate the invention and not in any sense to limit the manner in which the invention can be practiced. The parts and percentages recited therein and all through the specification, unless specifically provided otherwise, are by weight.

EXAMPLE I Melamine-Diacetone Acrylamide-Formaldehyde Resin Into a thermometer-liter flask equipped with mechanical stirrer, reflux condenser and thermometer there is introduced 1,500 grns. of 52% aqueous formaldehyde solution and 600 gms. of water. The pH of this solution is adjusted to 7-8 by the addition of 2.5 gms. of triethanol amine. Then there are added 1,240 gms. of melamine and 515 gms. of diacetone acrylamide. The resultant mixture is then heated to 90,C. and maintained at this temperature until tests show that a drop of this mixture when placed in a beaker of cold water (15C.) forms a slightly opaque or opalescent cloud. When this point is reached, sodium hydroxide solution is added to adjust the pH of the solution to 10.5-1 1.5. The reflux condenser is then replaced with a distillation condenser and the distillate removed under a reduced pressure of 25 inches of mercury to a temperature of 90C. The reaction is held at this temperature and reduced pressure until a resin is produced which has a gradient bar melt ing point of 200F. This resin may be easily ground when cool and does not sinter upon standing at room temperature. The yield of resin is found to be 2516- gms. The Stroke cure method shows a cure of 135 seconds at 330F. The addition of 3% benzoyl peroxide reduces the cure time by approximately 80%. The resin is moderately soluble in diallyl phthalate and triallyl cyanurate and slightly soluble in hydrocarbons such as styrene. It also exhibits very high solubility in water which is in contrast to the lack of water solubility in melamine resins prepared in an identical fashion but with the omission of the diacetone acrylamide. Upon testing, castings of the resin show excellent electrical resistance properties.

EXAMPLE ll Benzoguanamine-Diacetone Acrylamide-Formaldehyde Resin Into a 4-liter flask equipped with a reflux condenser, thermometer and mechanical stirrer, there is introduced 1,500 gms. of a 52% aqueous solution of formaldehyde and 600 grns of water. The pH of the solution is adjusted to 7.2-7.6 by the addition of 2.5 gms. of triethanol amine. Then 515 gms. of diacetone acrylamide and 1,830 gms. of benzoguanamine are added. The mixture is then heated to and held at this temperature until the free formaldehyde content of the solution analyzes to less than 2%. Then 1 l gms. of 10% sodium hydroxide solution is added to adjust the pH to the range of 10.5-11.5. The reflux condenser is then replaced with a distillation condenser and distillation effected at C. and a reduced pressure of 27 inches of mercury. This is continued until the melting point, determined by the gradient bar method, reaches F. The resin is then discharged from the flask and allowed to cool. The yield is 2721 gms. and the melting point is 188F. This resin shows no signs of curing after 5 minutes heating at 300F. However, upon addition of 3% benzoyl peroxide, the resin is cured in less than 20 seconds at 330F. to a rigid solid state. The uncured resin is not water soluble, but is completely miscible in diallyl phthalate and has improved solubility in hydrocarbons such as styrene as compared to the resin of Example l. Solutions of this resin in a solvent comprising equal parts of styrene and diallyl phthalate and containing 60% by weight resin cure with benzoyl peroxide to clear, almost colorless castings. However castings which employ diallyl phthalate as the only solvent are superior in color and strength to the castings in which the styrene-diallyl phthalate mixture is used. When the resin from this example is dissolved in 1,3- butyleneglycol dimethacylate to form a 50 solution by weight, and this solution mixed with parts titanium dioxide, 10 parts magnesium oxide and one part tertiarybutyl perbenzoate, a composition is produced having value as a top or decorative layer for polyester sheet or bulk molding material. When this material is cured by the application of heat and pressure, it is found to possess a Rockwell hardness on the E scale of approximately 85; while a polyester composition containing the same amounts of fillers by weight, was found to have a Rockwell hardness on the scale of approximately 65. This improvement in hardness is beneficial for many applications where abrasion resistance is very important. These castings also show excellent electrical resistance properties.

EXAMPLE lll Melamine-Acrylamide-Formaldehyde Resin Into a 4-liter flask equipped with a mechanical stirrer, reflux condenser and thermometer, there are added 1,500 gms. of 52% aqueous formaldehyde solution and 600 gms. of water. The pH of the solution is adjusted to 7-8 by the addition of 2.5 gms of triethanol amine. Then there are added 1,240 gms. of melamine and 217 gms. of acrylamide. The mixture is then heated to 90C. and maintained at this temperature until tests indicate that a drop of the reaction mixture when placed in a beaker of cold water forms a slightly opaque cloud. Then sufficient sodium hydroxide solution is added to adjust the pH of the solution to 10.5-11.5. The reflux condenser is replaced with a distillation condenser and distillation removed under a vacuum of 25 inches of water until a temperature of 90C. is reached. The reaction mixture is held at this temperature Ul'llll a product is obtained which has a gradient bar melting point of 194F. This resin may be easily ground when cool and does not sinter upon standing at room temperature. The yield is 2,215 gms. lts Stroke method cure of 155 seconds at 330F. is reduced approximately 75% by the addition of 0.5% benzoyl peroxide (based on weight of resin).

EXAMPLE 1V Benzoguanamine-Vinyl Methyl Ketone-Formaldehyde Resin Into a 4-liter flask equipped with a reflux condenser, thermometer and mechanical stirrer, there are introduced 1,500 gms. of 52% aqueous formaldhyde solution and 600 gms of water. The pl-l of the solution is adjusted to 7.2-7.6 with approximately 2.5 gms. of triethanol amine. Then 1,830 gms. of benzoguanamine and 213 gms. of vinyl methyl ketone are added. This mixture is heated to 90C. and held at this temperature until the free formaldehyde in the solution is below 2%. Then the pH is adjusted to 10.5-1 1.5 by the addition of 10% sodium hydroxide solution. The reflux condenser is replaced with a distillation condenser and the pressure is gradually reduced to 27 inches of Hg. The distillate is removed until the reaction mixture reaches a temperature of l20and this temperature is maintained until the melting point as determined by the gradient bar method reaches F. The resin is then discharged from the kettle and allowed to cool. A yield of 2,418 gms. is obtained. This resin shows no signs of curing after 5 minutes at 330F., but on the addition of 0.5% benzoyl peroxide, the resin cures to a rigid resin in less than 25 seconds at 330F.

EXAMPLE V Preparation of an Allylacetone-Melamine-Formaldehyde Resin Into a 4-liter resin flask equipped with a reflux condenser, thermometer and mechanical stirrer, is loaded 1,500 gms. (26 moles) of 52% aqueous formaldehyde and 600 gms. of water. The pH of this solution is adjusted to the proper range, 1,371 gms. (10.9 moles) of melamine and 532 gms. (5.44 moles) of allylacetone (l-hexene-S -one) are added to the resin flask and the reaction mixture heated to 90C. When 90C. is reached sufficient 10% sodium hydroxide (25gms.) is added to bring the pH to 11.5. A slight exothermic reaction is observed and the reaction mixture is maintained at 90C. for 5 minutes. When the 5 minute holding period is completed the reflux condenser is replaced with a distillation condenser and the pressure slowly reduced to 25 inches of mercury. The distillation is continued until the temperature reaches 65C. Then the pressure within the vessel is increased to 20 inches of Hg, and the temperature is raised to 90C. at which time the pressure is again slowly decreased to 26 inches of Hg while keeping the batch temperature at 90C. The batch is held at this temperature and pressure for one hour, then discharged to a cooling tray. The somewhat hygroscopic resin is found to have a gradient bar melting point of 180F. and a Stroke set time at 330F. of 180 seconds. When 3% dicumylperoxide is added to the resin, the set time at 330F. is decreased to less than 20 seconds. That the allylacetone had reacted with the methylol melamine is shown by the presence of strong carbonyl absorption at 1,715 cm in the infrared spec trum of the resin and by material balance calculations which show that 4l7gms. (4.28 moles) of allylacetone has reacted with the melamine-formaldehyde adduct or polymer. it is found by separate experiment that allylacetone does not react with formaldehyde alone at the pH of the above reaction, even if it is refluxed for several hours. Upon testing the resin product of this example is found to have excellent electrical resistance properties.

EXAMPLE Vl Preparation of an Allylarnine-Melaminc-Formaldehyde Resin Into the same apparatus as used in Example V is added 1,500 gms. (26 moles) of 52% aqueous formaldehyde and 600 gms. of water. The pH of this solution is adjusted to 7.4 with 3.5 gms. triethanolamine. Then 1.371 10.9 moles) gms. of melamine is added followed by 99.4 gms. (17.4 moles) of allylamine. As soon as the allylamine is added a substantial exotherm is noted. The batch is heated to 90C. and sufficient 10% sodium hydroxide (25 gms.) is added to adjust the pH to 11.6. As soon as the pH is obtained the pressure is reduced below atmospheric, and distillation continued at 16 inches of Hg to a batch temperature of 85C.. at which point the batch is discharged to cooling trays. The resultant resin is found to have a gradient bar melting point of 280F. and a set time by the Stroke method of less than seconds. From material balance calculations virtually all materials are accounted for. Consequently, all of the allylamine remains in the product. This is also reflected in the high melt point and short set time of the product which are much higher and much shorter respectively than unmodified melamine-formaldehyde resins.

The above procedure is repeated except that the allylamine is withheld until just prior to the reduction of pressure. The allylamine is added and heating continued for minutes before the pressure is reduced. Similar results are obtained as in the initial procedure.

When the above initial procedure is repeated twice using Z-aminopropene-l and p-vinyl aniline similar results are obtained.

EXAMPLE VIII The Preparation of an Acrylamine-Benzoguanaminc-Formaldehyde Resin Into the same apparatus used in Example I there is charged 1.300 grns. (22.5 moles) of52 /c formaldehyde and 500 gms. of water. The pH of this solution is adjusted to 7.3 with 2 gms. of triethanolamine. Then 1.300 gms. (6.9 moles) benzoquanamine and 355 gms. v

(5.0 moles) acrylamide are added and the reaction mixture heated to 90C. at which temperature it is held for 15 minutes. As soon as the holding period is completed 12 gms. of 10% sodium hydroxide is added. The

pH at this point is 10.0 to 1 1.0. The reflux condenser is replaced with a vacuum distillation condenser and receiver and distillation effected up to a resin temperature of 90C. under a reduced pressure of 28 inches of Hg at which point the pressure is further reduced to 25 inches of Hg and distillation continued to a resin temperature of 150C. When a batch temperature of 150C. is reached the resin is discharged into clean cooling pans. The melting point of this resin is found to be 215F. by the gradient bar method and the color is light yellow-green.

This material is found to have a set time by the Stroke method at 330F. in excess of 5 minutes. However, if the resin is blended with 3% benzoylperoxide or dicumyl peroxide, the set times are shortened to below seconds which indicates that complete cure can be very efficiently obtained through free redical addition reactions without further use of condensation curing mechanisms.

EXAMPLE 1X The Preparation of a Diacetoneacrylamide-Benzoguanamine-Furfural Resin Into the same apparatus used in Example I there is charged 2,033 gms. (21.15 moles) of fut'fural. 2.0 gms. triethanolamine. 400 gms. (2.36 moles) diacetoneacrylamide and 1.424 gms. (7.62) benzoguanamine. This mixture is heated to 100C. and held at this temperature for one hour. At the end of this period. 8.6 gms. or 10% NaOH is added and distillate removed under a reduced pressure of 28 inches of Hg and up to 100C. reaction temperature. It is held at 28 inches of Hg and 100C. for minutes and then discharged into a cooling pan. The yield is found to be 2,570 gms. of dark brown, almost black resin which is found to have a melting point of 190F. by the gradient bar method and a Stroke method set time in excess of 5 minutes at 330F. In this case the incorporation of 3% benzoylperoxide does not shorten the set time.

EXAMPLE x The Preparation of an Improved Polyester Molding Material with Improved Resistance to Humid Aging and Improved Abrasion Resistance The starting materials listed in the table below are blended in a ribbon mixer, then placed upon a differential two roll compounding mill with the front roll maintained at 200F. and the back roll maintained at 300F. As soon as the mixture melts and forms a homogeneous sheet, timing is begun and the sheet is kept on the roll for 30 45 seconds at which point it is stripped off the roll, cooled and the brittle product ground to a powder that will pass through an 8-mesh screen. Specimens cup molded from this powder at 350F. and 500 psi are found to possess the properties listed in the table. Specimens of this powder compression molded at 350F. and 2,0003,000 psi are found to have the properties listed in the following table:

TABLE Starting Materials: Parts Type 88 Polyester Resin 950 (Isophthalate-Propylene Glycol-Maleate: 2.5-3.5-1 molar ratio) Dicumyl peroxide 42 Lime 5 Calcium stcarate 40 Dark cotton 250 7TF|2 Asbestos 300 KH 31 Alumina 2000 Resin of Example I 300 Brown Umber 2.5 Red Orange 2767 1 Cadmium Yellow 2272 12 Hoover Brown 9827 l 1 White TiO-= R992 27 Molded Properties 1 Min. Deflection .073 Density .819 Moisture .0370 Sp. Gravity 1.84 Dielectric Strength 368 VPM*-l SE-O 1/16" 00-0*-2 Test at 200F.. 20 kv. 1 hr. Good*-3 Flcxural Strength (ASTM D790) 8830 psi Western Electric IR (ASTM D2571 Infinite as is After exposure to 140F. and 977: 2 X 10* *-1 According to ASTM \est D149 (vpm units are volts per mil of thickness) 2 0-0-0 means the test sample doesn't burn. glow or drip. It passes the Underwriters Laboratories Test S-492-A in thicknesses of 1/16" for non-burning material.

*-3 This test is erlormcd on a /n" thick X 4" disk which withstands 20 kilovolts at 200F, for at least one hour.

EXAMPLE X1 Melamine-vinylmethyl Ketone Formaldehyde Resin Into a 4-liter flask equipped with a reflux condenser, thermometer and mechanical stirrer, there are introduced 1,500 gms. (26 moles) of 52% aqueous formaldehyde solution and 600 gms of water. The pH of the solution is adjusted to 7.4-7.7 with approximately 3.5 gms. of triethanolamine. Then 1,371 gms. (10.9 moles) of melamine and 98 gms. (1.40 moles) of vinylmethyl kctone are added. This mixture is heated to C. and held at this temperature for 20 minutes. The pH of the solution is then adjusted to l 1.0-1 1.7 by the addition of sodium hydroxide solution. The temperature is held at 90C. for 10 minutes. the reflux condenser is replaced with a distillation condenser, and the pressure is gradually reduced to 25 inches of Hg. The distillate is removed until the reaction mixture reaches a temperature of 90C. If desired the vacuum may then be decreased to 22 inches of Hg. The resin is then maintained at 90C. and 22 inches to 25 inches of Hg until the melting point, as determined by the gradient bar method, is over 180F. The resin is then discharged from the resin flask and allowed to cool. A yield of 2,241 gms. is obtained and the resin is found to have a gradient bar melting point of 215F. and a stroke set time at 330F. of 61-62 seconds. However, the addition of 3% benzoyl peroxide or dicumyl peroxide is found to decrease the set time to 20 seconds.

EXAMPLE XII The procedure of Example X is repeated with similar results using as the polyester one prepared by the following procedure:

A 4-liter 304-stainless steel kettle is equipped with a thermometer, steam jacketed fractionating column measuring inches high, having an inside diameter of 0.750 inches and packed with ceramic saddles, nitrogen inlet tube and agitator. A water trap and condenser are placed at the top of the fractionating column to collect and remove distillate water that passes through the column. To the kettle there is charged 1,520 grns. moles) of propylene glycol and 997 gms. (6 moles) of isophthalic acid. This mixture is heated under a slow stream of nitrogen gas to reflux. When the temperature reaches 187C, water begins to collect in the overhead trap. Heating is continued until the batch temperature has risen to 192C, the acid number is found to be 4.25 and a total of 222 gms. of distillate has been collected. At this point the batch is cooled to 100C and 1,176 gms. of maleic anhydride (12 moles) is quickly added. The mixture is heated again, under a steady nitrogen flow, to 218, and held to this temperature until. the acid number has again fallen to 19.5 and 197 gms. of additional distillate has been collected. When this condition is reached, the steam jacketed column is replaced with simple vacuum distillation adapter, condenser, and receiver; and distillable material is removed from the batch at 29 inches of Hg vacuum (approximately 2.5 cm of Hg absolute pressure) for one hour. The vacuum is then released and the resin poured into a clean stainless steel pan to cool. The yield of clear honey-colored resin is found to be 3,108 gms. This is found to have a gradient bar melting point of 131F, an acid number of 15.2, and a hydroxyl number of 54. By end group analysis the number average molecular weight is found to be 1,624, whereas the molecular weight by cryoscopy in p-diozane is found to be 1,476. A 50% styrene solution of the above resin is found to have a brooktield viscosity at C of 280 cps.

As stated above when this resin is used as the polyester resin in the procedure of Example X, similar improved properties are noted.

EXAMPLE Xlll An unsaturated polyester resin is prepared using the equipment described in Example X11. To the reactor kettle there is charged 1,520 gms. (20 moles) of propylene glycol and 846 gms. (5.1 moles) of isophthalic acid.

This mixture is heated to reflux under a slow stream of nitrogen gas until the acid number is 5.0 and 200 gms. of distillate has been collected. During this period the jacket of the reflux condenser is set at 5 psig of steam pressure. The batch is then cooled to C and 1,266 gms. of maleic anhydride (12.9 moles) is added The mixture is heated slowly to 218C over a period of 5 hours while additional distillate is collected. When approximately gms. of additional distillate has been collected and the acid number has dropped to approximately 43, the reflux condenser is removed and is replaced with a vacuum distillation adapter, condenser and receiver. Distillable material is removed by heating the reaction mass to 198to 219C for 1 hour at 28 inches of Hg vacuum and then the resin product is discharged to a cleam stainless steel pan to cool. The yield of the light-yellow resin is found to be 3,114 gms. and to have a gradient bar melting point of 1 18F. The acid number and hydroxyl number are found to be 20 and 64, respectively; the molecular weight is found by end group analysis and by cryoscopy in p-dioxane to be 1,331 and 1,193 respectively. When a 50% solution of this resin in styrene is prepared, it is found to have a Brookfield viscosity at 25C of 145 centipoise.

This resin is used as the unsaturated polyester component in the molding fomulation described in Example X and the resin of Example 11 is used in place of the resin of Example 1. Improved properties similar to those described in Example X are noted.

Similar results are also noted when the abovedescribed polyester resin is used with the resins of Examples lll X and XI respectively.

EXAMPLE XIV An unsaturated polyester resin is prepared using the equipment described in Example Xll. To the reactor kettle there is charged 1,710 gms. (16,5 moles) of neopentyl glycol and 132 gms. (1.43 moles) of glycerine.

The mixture is heated under a slow stream of nitrogen gas until all the neopentyl glycol has melted and dissolved in the glycerine. As soon as this occurs 806 gms. (4.86 moles) of isophthalic acid is added and the mixture is heated to reflux with 5 lbs. of steam pressure in the jacket of the column. At approximately C. (batch temperature) water begins to collect in the trap. When the batch temperature has risen to 210C, 140 gms. of water has been collected and the acid number is found to be 45.6 mgKOH/gm of resin. The batch is cooled to 100C and 1,289 grns. (13.14 moles) of maleic anhydride and 2.0 gms. hydroquinone are added to the batch. This mixture is then heated slowly to 218C under a steady stream of nitrogen while water continues to be taken off from the overhead condenser. When 218C is reached, 209 gms. of additional water is removed and the acid number is found to be 51.3. At this point the reflux condenser is removed and replaced by a simple distillation adapter, vaccum condenser and receiver, and 28 inches of Hg vacuum is applied to the batch. The resin is heated thus for three hours holding the vacuum between 28 inches and 28.7 inches of Hg while the temperature of the batch slowly rises from 184C to 215C. The product is discharged to a clean stainless steel pan to cool. The yield of the pale strawcolored resin is found to be 3,469 gms. This resin is found to possess a gradient bar melting point of 125F. an acid number of 17.5, and a hydroxyl number of 154. A 50% styrene solution of this resin is found to have a Brookfield viscosity at 25 C of 1,420 centipoise. The molecular weight of this resin is determined by end group analysis to be 654.

This resin is used as the unsaturated polyester component in the molding formulation described in Example X. Improved properties similar to those described in Example X are noted.

Similar results are also noted when the abovedescribed polyester resin is used in the molding formulation of Example X together with the resins of Examples Ill-1X and XI respectively.

EXAMPLE xv The procedure of Example X is repeated a number of times with similar results using in place of the 88 polyester resin an equal weight respectively of:

a. ethylene glycol-maleate (1-1 molar ratio) polyester (acid and hydroxyl numbers 18 and 46 respectively) b. propylene glycol-maleate (11 molar ratio) polyester (acid and hydroxyl numbers 14 and 63 respectively) c. propylene glycol itaconate (ll molar ratio) polyester (acid and hydroxyl numbers 21 and 38 respectively) d. isophthalate-ethylene glycol-fumarate (2-3-1 molar ratio) polyester (acid and hydroxyl numbers 28 and 49 respectively) e. o-phthalate-diethylene glycol-maleate (2.5-3.5-1 molar ratio) polyester (acid and hydroxyl numbers 12 and 37 respectively) f. succinate-propylene glycol-maleate (2.5-3.5-1 molar ratio) polyester (acid and hydroxyl numbers 22 and 42 respectively) The resin mixtures of this invention are advantageously cured at 25-400F., preferably 300-350F.

While certain features of this invention have been described in detail with respect to various embodiments thereof, it will, of course, be apparent that other modifications can be made within the spirit and scope of this invention and it is not intended to limit the invention to the exact details shown above except insofar as they are defined in the following claims:

The invention claimed is:

l. A process for producing and curing a molding resin composition of improved curing and electrical resistance characteristics comprising the steps of reacting in a liquid medium:

a. a triazine compound selected from the class consisting of melamine and benzoguanamine;

b. an aldehyde selected from the class consisting of formaldehyde, acetaldehyde, chloracetaldehyde and furfuraldehyde;

c. a vinyl compound having the formula wherein R is selected from the class consisting of hydrogen and an alkyl group of 1-4 carbon atoms, and X is a radical selected from the class consisting of:

H II R -CNH -c1 mc on on ca -c H NH -CHNH;-

2 2 NHZ c011 cru cn and 0 -CH 'c'cH 2 3 the proportion of said vinyl compound being 0.05-100 moles per mole of said triazine compound, and the proportion of said aldehyde being 0.5-6 moles per mole of said triazine compouund with an additional 0.5-5 moles of aldehyde per mole of said vinyl compound; said reaction being conducted at a temperature of 60-100C. and a pH in the range of 7-12 and the water being eventually removed from the reaction mass by heating under reduced pressure until the resin product forms a brittle solid mass upon cooling; admixing said resin product with 5-99 percent by weight of an unsaturated polyester prepared by the condensation of a glycol with a dibasic carboxylic acid, at least 25% of the dibasic acid component being an unsaturated aliphatic dibasic acid; and thereafter curing the resultant resin mixture at a temperature of 25400F. in intimate mixture with 0.05-10 percent by weight of a peroxy or azo free-radical generating catalyst.

2. The process of claim 1 in which said liquid medium is water.

3. The process of claim 2 in which said aldehyde is formaldehyde.

4. The process of claim 3 in which said triazine compound is melamine.

5. The process of claim 4 in which the proportion of said vinyl compound is 0.1-10 moles per mole of melamine and the proportion of said aldehyde is 1.5-2.5 moles per mole of melamine plus an additional 1.5-3 moles per mole of said vinyl compound.

6. The process of claim 5 in which said reacting is effected at a temperature of -95C., the pH is initially 7-8 and prior to the complete removal of water the pH is adjusted to 10-12.

7. The process of claim 6 in which said vinyl compound is diacetone acrylamide.

8. The process of claim 6 in which said vinyl compound is acrylamide.

9. The process of claim 6 in which said vinyl compound is vinylmethyl ketone.

10. The process of claim 6 in which said vinyl compound is allyl amine.

11. The process of claim 3 in which said triazine compound is benzoguanamine.

12. The process of claim 11 in which said vinyl compound is diacetone acrylamide.

13. The process of claim 1 in which 0.1-5 percent by weight of a peroxy free radical generating catalyst is added to the resin composition and the mixture is cured at a temperature of 300350F.

14. The process of claim 1 in which said catalyst is a peroxide selected from the class of benzoyl and dicumyl peroxides.

15. The process of claim 1 in which said curing temperature is 300-350F.

16. A resin of improved curing and electrical resistance properties produced according to the process of claim 1. I

polyester mixture also contains 5-50 percent by weight, based on total resin-polyester-stryene weight, of styrene prior to said curing step.

21. The process of claim 1 in which said resinpolyester mixture also contains 5-50 percent by weight, based on total resin-polyester-diallyl phthalate weight, of diallyl phthalate prior to said curing step.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,887,637 DATED June 3, 1975 INVENTOMS): Phillip A. Waitkus It is certified that error appears in the ab0ve-identified patent and thatesaid Letters Patent amhembycmmcmdasdwwnbdow:

Column 2, line 8, the word "reached" should be reacted Column 5, line 31, before "general" insert Column 14, line l-2, correct the last formula to read 0 ll CCH2CH3 Signed and Sealed this twenty-fifth Day Of November 1975 I [SEAL] Attest:

- RUTH C. MASON Commissioner ufPatents and Trademarks 

1. A PROCESS FOR PRODUCING AND CURING A MOLDING RESIN COMPOSITION OF IMPROVED CURING AND ELECTRICAL RESISTANCE CHARACTERISTICS COMPRISING THE STEPS OF REACTING IN A LIQUID MEDIUM: A. A TRIAZINE COMPOUND SELECTED FROM THE CLASS CONSISTING OF MELAMINE AND BENZOGUANAMINE; B. AN ALDEHYDE SELECTED FROM THE CLASS CONSISTING OF FORMALDEHYDE, ACETALDEHYDE, CHLORACETALDEHYDE AND FURFURALDEHYDE; C. A VINYL COMPOUND HAVING THE FORMULA
 1. A process for producing and curing a molding resin composition of improved curing and electrical resistance characteristics comprising the steps of reacting in a liquid medium: a. a triazine compound selected from the class consistinG of melamine and benzoguanamine; b. an aldehyde selected from the class consisting of formaldehyde, acetaldehyde, chloracetaldehyde and furfuraldehyde; c. a vinyl compound having the formula
 2. The process of claim 1 in which said liquid medium is water.
 3. The process of claim 2 in which said aldehyde is formaldehyde.
 4. The process of claim 3 in which said triazine compound is melamine.
 5. The process of claim 4 in which the proportion of said vinyl compound is 0.1-10 moles per mole of melamine and the proportion of said aldehyde is 1.5-2.5 moles per mole of melamine plus an additional 1.5-3 moles per mole of said vinyl compound.
 6. The process of claim 5 in which said reacting is effected at a temperature of 85*-95*C., the pH is initially 7-8 and prior to the complete removal of water the pH is adjusted to 10-12.
 7. The process of claim 6 in which said vinyl compound is diacetone acrylamide.
 8. The process of claim 6 in which said vinyl compound is acrylamide.
 9. The process of claim 6 in which said vinyl compound is vinylmethyl ketone.
 10. The process of claim 6 in which said vinyl compound is allyl amine.
 11. The process of claim 3 in which said triazine compound is benzoguanamine.
 12. The process of claim 11 in which said vinyl compound is diacetone acrylamide.
 13. The process of claim 1 in which 0.1-5 percent by weight of a peroxy free radical generating catalyst is added to the resin composition and the mixture is cured at a temperature of 300*-350*F.
 14. The process of claim 1 in which said catalyst is a peroxide selected from the class of benzoyl and dicumyl peroxides.
 15. The process of claim 1 in which said curing temperature is 300*-350*F.
 16. A resin of improved curing and electrical resistance properties produced according to the process of claim
 1. 17. The process of claim 1 in which said unsaturated polyester resin is an ethylene glycol-maleate resin.
 18. The process of claim 1 in which said unsaturated polyester resin is a propylene glycol-maleate resin.
 19. The process of claim 1 in which said unsaturated polyester resin is an isophthalate-propylene glycol-maleate resin.
 20. The process of claim 1 in which said resin-polyester mixture also contains 5-50 percent by weight, based on total resin-polyester-stryene weight, of styrene prior to said curing step. 